Dithiinetetra(thio)carboximides

ABSTRACT

The present invention relates to novel dithiinetetra(thio)carboximides, to processes for preparing these compounds, to compositions comprising these compounds, and to the use thereof as biologically active compounds, especially for control of harmful microorganisms in crop protection and in the protection of materials and as plant growth regulators.

The present invention relates to novel dithiinetetra(thio)carboximides, to processes for preparing these compounds, to compositions comprising these compounds, and to the use thereof as biologically active compounds, especially for control of harmful microorganisms in crop protection and in the protection of materials and as plant growth regulators.

Dithiinetetracarboximides are already known. It is likewise known that these dithiinetetracarboximides can be used as anthelmintics to counteract internal parasites in animals, especially nematodes, and have insecticidal action (cf. U.S. Pat. No. 3,364,229). It is also known that particular dithiinetetracarboximides have antibacterial action and have a certain effect against organisms which cause human mycoses (cf. Il Farmaco 2005, 60, 944-947). It is additionally known that dithiinetetracarboximides can be used as pigments in electrophotographic photoreceptors or as dyes in coatings and polymers (cf. JP-A 10-251265, PL-B 143804).

Since the ecological and economic demands made on modern active ingredients, for example fungicides, are increasing constantly, for example with respect to activity spectrum, toxicity, selectivity, application rate, formation of residues and favourable manufacture, and there can also be problems, for example, with resistances, there is a constant need to develop novel fungicidal compositions which have advantages over the known compositions at least in some areas.

Novel dithiinetetra(thio)carboximides of the formula (I)

have now been found, in which

-   X¹ is O or S, -   X² is O or S, -   X³ is O or S, -   R¹ and R² are the same or different and are each hydrogen,     optionally mono- or poly-halogen-, —OR³—, —COR⁴-substituted     C₁-C₈-alkyl, optionally mono- or poly-halogen-, —C₁-C₄-alkyl- or     —C₁-C₄-haloalkyl-substituted C₃-C₇-cycloalkyl, in each case     optionally mono- or poly-halogen-, —C₁-C₄-alkyl-, —C₁-C₄-haloalkyl-,     —COR⁴— or -sulphonylamino-substituted aryl or aryl-(C₁-C₄-alkyl), -   R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl or optionally mono-     or poly-halogen-, —C₁-C₄-alkyl- or —C₁-C₄-haloalkyl-substituted     aryl, -   R⁴ is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy,     and the agrochemically active salts thereof.

The salts obtainable in this way likewise have fungicidal and/or plant growth-regulating properties.

The inventive dithiinetetra(thio)carboximides may optionally be present as mixtures of different possible isomeric forms, especially of stereoisomers, for example, E and Z isomers, threo and erythro isomers, and optical isomers, but if appropriate also of tautomers. Both the E and Z isomers, and the threo and erythro isomers, and also the optical isomers, any desired mixtures of these isomers, and the possible tautomeric forms are claimed.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-a)

in which R¹ and R² are each as defined above.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-b)

in which R¹ and R² are each as defined above.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-c)

in which R¹ and R² are each as defined above.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-d)

in which R¹ and R² are each as defined above.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-e)

in which R¹ and R² are each as defined above.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-f)

in which R¹ and R² are each as defined above.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-g)

in which R¹ and R² are each as defined above.

One subgroup of the inventive dithiinetetra(thio)carboximides is characterized by the formula (I-h)

in which R¹ and R² are each as defined above.

The inventive dithiinetetra(thio)carboximides are defined in general terms by the formulae (I) or (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g) and (I-h). Preferred radical definitions for the formulae specified above and below are given below. These definitions apply equally to the end products of the formula (I) and to all intermediates (see also below under “Illustrations of the processes and intermediates”).

-   R¹ and R² are preferably the same or different and are preferably     each hydrogen, optionally mono- or poly-fluorine-, -chlorine-,     -bromine-, —OR³—, —COR⁴-substituted C₁-C₆-alkyl, optionally mono- or     poly-chlorine-, -methyl- or -trifluoromethyl-substituted     C₃-C₇-cycloalkyl, in each case optionally mono- or poly-fluorine-,     -chlorine-, -bromine-, -methyl-, -trifluoromethyl-, —COR⁴—,     -sulphonylamino-substituted phenyl or phenyl-(C₁-C₄-alkyl). -   R¹ and R² are more preferably the same or different and are more     preferably each hydrogen, optionally mono- or poly-fluorine-,     -chlorine-, -hydroxyl-, -methoxy-, -ethoxy-, -methylcarbonyloxy-,     -carboxyl-substituted C₁-C₄-alkyl, optionally mono- or     poly-chlorine-, -methyl- or -trifluoromethyl-substituted     C₃-C₇-cycloalkyl, in each case optionally mono- to tri-fluorine-,     -chlorine-, -bromine-, -methyl-, -trifluoromethyl-, —COR⁴—,     -sulphonylamino-substituted phenyl, benzyl, 1-phenethyl, 2-phenethyl     or 2-methyl-2-phenethyl. -   R¹ and R² are even more preferably the same or different and are     even more preferably each hydrogen, methyl, ethyl, n-propyl,     isopropyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, in each case     optionally chlorine-, methyl- or trifluoromethyl-substituted     cyclopropyl or cyclohexyl. -   R¹ and R² are especially preferably both methyl. -   R³ is preferably hydrogen, methyl, ethyl, methylcarbonyl,     ethylcarbonyl or optionally mono- or poly-fluorine-, -chlorine-,     -methyl-, -ethyl-, -n-propyl-, -isopropyl- or     -trifluoromethyl-substituted phenyl. -   R³ is more preferably hydrogen, methyl, methylcarbonyl or phenyl. -   R⁴ is preferably hydroxyl, methyl, ethyl, methoxy or ethoxy. -   R⁴ is more preferably hydroxyl or methoxy.

A further embodiment of the present invention relates to compounds of the formula (I) or (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g) and (I-h) in which R¹ and R² are each methyl.

A further embodiment of the present invention relates to compounds of the formula (I) or (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g) and (I-h) in which R¹ and R² are each ethyl.

A further embodiment of the present invention relates to compounds of the formula (I) or (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g) and (I-h) in which R¹ and R² are each n-propyl.

A further embodiment of the present invention relates to compounds of the formula (I) or (I-a), (I-b), (I-c), (I-d), (I-e), (I-f), (I-g) and (I-h) in which R¹ and R² are each isopropyl.

Among these, emphasis is given to the compound of the formula (I-a) in which R¹ and R² are each methyl.

Among these, emphasis is given to the compound of the formula (I-b) in which R¹ and R² are each methyl.

Among these, emphasis is given to the compound of the formula (I-c) in which R¹ and R² are each methyl.

The radical definitions and explanations given above in general terms or stated within preferred ranges can, however, also be combined with one another as desired, i.e. including between the particular ranges and preferred ranges. They apply both to the end products and, correspondingly, to the precursors and intermediates. In addition, individual definitions may not apply.

Preference is given to those compounds of the formula (I) in which each of the radicals have the abovementioned preferred definitions.

Particular preference is given to those compounds of the formula (I) in which each of the radicals have the abovementioned more preferred definitions.

Illustration of the Processes and Intermediates

Process A

The dithiinetetra(thio)carboximides of the formula (I) can be prepared by in a first stage reacting succinic monoamides of the formula (VI)

in which R is R¹ or R², which are each as defined above, with an excess of thionyl chloride, optionally in the presence of a diluent, then removing the excess of thionyl chloride and converting the product mixture thus obtained, in a second stage, in an organic solvent or a mixture of an organic solvent and water, optionally in the presence of a phase transfer catalyst, and finally isolating the dithiinetetra(thio)carboximides of the formula (I) by chromatography processes.

The succinic monoamides of the formula (VI) used as starting materials are known or can be obtained in a known manner.

The amount of thionyl chloride in the first step of the process according to the invention is between 2 and 100 mol per mole of succinic monoamide of the formula (VI). Preference is given to using between 4 and 50 mol, particular preference to using amounts between 10 and 40 mol, per mole of succinic monoamide of the formula (VI).

The reaction temperature in the first step of the process according to the invention may be varied within wide limits and is between 0° C. and 150° C. To achieve satisfactory space-time yields, operating temperatures are preferably between 20° C. and 120° C.; more preferably between 30° C. and 100° C.

The reaction time in the first step of the process according to the invention is between 10 min. and 24 h. Preference is given to operating for between 30 min. and 6 h, more preferably between 1 and 4 h.

The first step of the process according to the invention can optionally be performed in the presence of a diluent which is very substantially inert under the reaction conditions. Examples of such diluents include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, octane, isooctane, chlorinated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, mesitylene, ethylbenzene, anisole, chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, nitriles such as acetonitrile, propionitrile, butyronitrile, esters such as methyl acetate and ethyl acetate. Preference is given to working in toluene, xylene, mesitylene, ethylbenzene, chlorobenzene, 1,2-dichlorobenzene, or without diluent.

The thionyl chloride can in principle be removed by hydrolysis with water. Preference is given to removing the thionyl chloride by distillative removal under reduced pressure.

Any diluent present can likewise be distilled off under reduced pressure and, if desired, replaced by another solvent

In the second step of the process according to the invention, the residue obtained after removal of the excess thionyl chloride and, if appropriate, of the diluent is dissolved in a new diluent and converted to the dithiinetetracarboximides of the formula (I) by heating in this solvent. The reaction mixture is preferably stirred during this time.

In the second step of the process according to the invention, organic solvents or solvent mixtures are used. Either these solvents are at least partly miscible with water, or phase transfer catalysts are used in addition.

Suitable diluents for the second step of the process according to the invention are specifically water, dimethyl sulphoxide, sulpholane, alcohols, for example methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, cyclopentanol, cyclohexanol, ethylene glycol, ethylene glycol monomethyl ether, hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane, toluene, xylenes, mesitylene, chlorbenzene, dichlorobenzene, nitrobenzene, esters such as methyl acetate, ethyl acetate, amides such as formamide, N,N-dimethylformamide; N,N-dimethylacetamide, N-methylpyrrolidone, ethers such as methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, pinacolone, carboxylic acids such as formic acid, acetic acid, propionic acid, or mixtures of these diluents.

The at least partly water-miscible diluents used are preferably dimethyl sulphoxide, methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, cyclohexanol, ethylene glycol, methyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, 1,4-dioxane, acetonitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetic acid or mixtures of these diluents.

It is even more preferable to use mixtures of water and methanol, ethanol, propanol, isopropanol, -butanol, 2-butanol, isobutanol, 1-pentanol, methyl acetate, tetrahydrofuran, 1,4-dioxane, acetonitrile, acetone, acetic acid.

Suitable diluents having only very slight or zero water miscibility for the second step of the process according to the invention are specifically hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane, octane, isooctane, toluene, xylenes, mesitylene, ethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, water or mixtures of these diluents.

It is preferable to use hexane, heptane, cyclohexane, methylcyclohexane, octane, isooctane, toluene, xylenes, mesitylene, chlorobenzene, dichlorobenzene, water or mixtures of these diluents.

It is even more preferable to use mixtures of water and toluene, xylene or chlorobenzene.

The mixing ratio of water to organic solvent can be varied within wide limits from, for example, 9:1 to 1:9.

The phase transfer catalysts (PTC) may in principle be any compounds known to be effective as PTCs. Such compounds may, for example, be phase transfer catalysts from the group of the quaternary ammonium salts or the quaternary phosphonium salts.

This phase transfer catalyst preferably has the general formula (X)

in which

-   R⁵, R⁶, R⁷ and R⁸ are the same or different and are each     independently straight-chain or branched C₁-C₂₈-alkyl, C₆-C₁₀-aryl     or benzyl, -   X is halogen, hydrogensulphate, sulphate, dihydrogenphosphate,     hydrogenphosphate, phosphate or acetate (preferably bromine,     chlorine, fluorine, hydrogensulphate, sulphate, phosphate and     acetate), -   A is N or P.

Examples of such phase transfer catalysts include tetrabutylammonium fluoride, chloride, bromide, iodide, acetate or hydrogensulphate, tetraethylammonium bromide or iodide, methyltributylammonium chloride, bromide, iodide, acetate or hydrogensulphate, benzyldodecyldimethylammonium chloride or bromide, benzyltriethylammonium bromide or chloride, dodecyltrimethylammonium chloride or bromide, tetradecyltrimethylammonium chlorid or bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, tetraoctylammonium bromide or chloride, didecyldimethylammonium chloride or bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide and ethyltriphenylphosphonium acetate.

In addition, it is also possible to use phase transfer catalysts such as 4-dialkylaminopyridinium salts or hexaalkylguanidinium salts.

Preference is given to using methyltrioctylammonium chloride (trade name Aliquat® 336; present in a mixture with methyltridecylammonium chloride), methyltridecylammonium chloride or bromide, tetraoctylammonium bromide or chloride, dodecyltrimethylammonium chloride or bromide, tetradecyltrimethylammonium chloride or bromide, didecyldimethylammonium chloride or bromide, and benzyldodecyldimethylammonium chloride or bromide as phase transfer catalysts.

The amount of phase transfer catalyst in the process according to the invention can be varied within wide limits. The amount is preferably between 0.5 and 25 g per mole of succinamide of the formula (VI), more preferably between 1 and 10 g per mole of succinamide of the formula (VI).

The reaction temperature in the second step of the process according to the invention may be varied within wide limits and is between 0° C. and 200° C. Preference is given to working at temperatures between 20° C. and 150° C., more preferably between 30° C. and 130° C.

The reaction time in the second step of the process according to the invention is between 5 min. and 24 h. Preference is given to operating for between 30 min. and 12 h, more preferably between 1 and 8 h.

To isolate the dithiinetetra(thio)carboximides, the substance prepared by the process described is dissolved while heating in a suitable solvent, for example acetonitrile, butyronitrile, tetrahydrofuran, 2-methyltetrahydrofuran or 1,4-dioxane, and separated on a preparative reversed-phase HPLC column with an aqueous eluent consisting of water or 1% formic acid and acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran or 1,4-dioxane. Preference is given to using 1% formic acid and acetonitrile with a flow rate of 10 to 100 ml/min, depending on the column dimensions. The detection is effected by UV absorption. The fractions of the isolated components are analysed by HPLC in order to identify the fraction of the title compound. On completion of assignment, the target substance is isolated by means of solid phase extraction.

The substance prepared by the process described is preferably dissolved while heating in tetrahydrofuran or 1,4-dioxane and separated on a preparative reversed-phase HPLC column with an aqueous eluent consisting of 1% formic acid and acetonitrile with a flow rate of 10 to 100 ml/min, depending on the column dimensions. The detection is effected by UV absorption. The fractions of the isolated components are analysed by HPLC in order to identify the fraction of the title compound. On completion of assignment, the target substance is isolated by means of solid phase extraction.

The title compound can also be isolated by supercritical fluid chromatography (SFC). The substance prepared by the process described is dissolved in a suitable solvent, preferably 1,4-dioxane, and separated on a preparative SFC column with a mixture of CO₂ and methanol, tetrahydrofuran or 1,4-dioxane, preferably CO₂ and 1,4-dioxane. The detection is effected by UV absorption. The fraction of the target compound is concentrated under reduced pressure or freeze-dried.

The title compound is preferably isolated by means of SFC, by dissolving the substance prepared by the process described in 1,4-dioxane and separating it on a preparative SFC column with a mixture of CO₂ and 1,4-dioxane. The detection is effected by UV absorption. The fraction of the target compound is concentrated under reduced pressure or freeze-dried.

Process B

The dithiinetetra(thio)carboximides of the formula (I) can also be prepared by reacting dichloromaleimides of the formula (VII)

in which R² and X³ are each as defined above with dichloromaleimides of the formula (VIII)

in which R¹, X¹ and X² are each as defined above, and with an inorganic thiosulphate in a solvent or solvent mixture.

Some of the dichloromaleimides of the formulae (VII) and (VIII) required as starting materials are known. They can be obtained, for example, by reacting N-substituted maleimides with a thionating reagent (e.g. Lawesson's re-agent) in the presence of a diluent (e.g. toluene) and subsequently reacting the thioimides thus obtained with a chlorinating agent (e.g. thionyl chloride) in the presence of a base (e.g. pyridine) and in the presence of a diluent (e.g. methylene chloride) (cf. Example 3).

The thiosulphate used may in principle be any soluble inorganic thiosulphate salts, for example lithium thiosulphate, sodium thiosulphate, potassium thiosulphate, caesium thiosulphate, magnesium thiosulphate or ammonium thiosulphate. Preference is given to using sodium thiosulphate, potassium thiosulphate or ammonium thiosulphate, more preferably sodium thiosulphate or ammonium thiosulphate. It will be appreciated that it is also possible to use mixtures of these salts. The terms “thiosulphate” and “thiosulphate salt” shall, to the extent that they exist, also include hydrates of these salts.

The thiosulphate is used in amounts between 1.1 and 1.8 mol per mole (total amount) of dichloromaleimide of the formulae (VII) and (VIII). Preferred amounts are between 1.2 and 1.7 mol of thiosulphate, more preferably between 1.3 and 1.6 mol of thiosulphate.

The thiosulphate can be added to the reaction mixture in solid form or as a solution, for example in water. If appropriate, the thiosulphate can also be added in liquid form as a melt. For example, sodium thiosulphate pentahydrate melts between 45° C. and 50° C. Preference is given to adding the thiosulphate as a solution in water.

The reaction temperature of the process according to the invention can be varied within wide limits and is between 0° C. and 200° C. To achieve satisfactory space-time yields, operating temperatures are preferably between 20° C. and 180° C.; more preferably between 30° C. and 150° C.

The reaction time of the process according to the invention is between 10 minutes and 24 hours. Preference is given to operating for between 30 minutes and 12 hours, more preferably between 1 and 6 hours.

Suitable solvents for the process according to the invention are water, dimethyl sulphoxide, sulpholane, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, cyclopentanol, cyclohexanol, ethylene glycol, ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate, amides such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethers such as tetrahydrofuran, dioxane, nitrites such as acetonitrile, propionitrile, butyronitrile, benzonitrile, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, pinacolone, or mixtures of these diluents.

Preference is given to using water, dimethyl sulphoxide, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, cyclohexanol, ethylene glycol, methyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, 1,4-dioxane, acetonitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, or mixtures of these diluents.

It is even more preferable to use mixtures of water and methanol, ethanol, propanol, isopropanol, methyl acetate, tetrahydrofuran, 1,4-dioxane, acetonitrile or acetone.

The compounds of the general formula (I) obtainable by the processes according to the invention can be converted to acid addition salts or metal salt complexes. For preparation of physiologically acceptable acid addition salts of the compounds of the general formula (I), the following acids are preferred options: hydrohalic acids, for example hydrochloric acid and hydrobromic acid, especially hydrochloric acid, and also phosphoric acid, nitric acid, sulphuric acid, mono- and bifunctional carboxylic acids and hydroxycarboylic acids, for example acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and sulphonic acids, for example p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid. The acid addition salts of the compounds of the general formula (I) can be obtained in a simple manner by customary methods for forming salts, for example by dissolving a compound of the general formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtering them off, and can optionally be purified by washing with an inert organic solvent. For preparation of metal salt complexes of the compounds of the general formula (I), preferred options are salts of metals of main groups II to IV and of transition groups I and II and IV to VIII of the Periodic Table, for example copper, zinc, manganese, magnesium, tin, iron and nickel. Useful anions of the salts include those which are preferably derived from the following acids: hydrohalic acids, for example hydrochloric acid and hydrobromic acid, and also phosphoric acid, nitric acid and sulphuric acid. The metal salt complexes of compounds of the general formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the general formula I. Metal salt complexes can be isolated in a known manner, for example by filtering them off, and can optionally be purified by recrystallization.

The present invention further relates to a composition for controlling unwanted microorganisms, comprising the inventive active ingredients. Said composition is preferably a fungicidal composition which comprises agriculturally suitable auxiliaries, solvents, carriers, surfactants or extenders.

The invention also relates to a method for controlling unwanted microorganisms, characterized in that the inventive active ingredients are applied to the phytopathogenic fungi and/or their habitat.

According to the invention, a carrier is a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seed. The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture.

Useful solid or liquid carriers include: for example ammonium salts and natural rock dusts, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock dusts, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils, and derivatives thereof. Mixtures of such carriers can likewise be used. Useful solid carriers for granules include: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and also granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.

Useful liquefied gaseous extenders or carriers are those liquids which are gaseous at standard temperature and under standard pressure, for example aerosol propellants such as halohydrocarbons, and also butane, propane, nitrogen and carbon dioxide.

In the formulations, it is possible to use tackifiers such as carboxymethylcellulose, and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further additives may be mineral and vegetable oils.

If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and also water.

The inventive compositions may additionally comprise further components, for example surfactants. Useful surfactants are emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Examples of these are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose. The presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and when application is effected in water. The proportion of surfactants is between 5 and 40 percent by weight of the inventive composition.

It is possible to use dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

If appropriate, it is also possible for other additional components to be present, for example protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, sequestrants, complexing agents. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.

The inventive compositions and formulations generally contain between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, more preferably between 0.5 and 90% by weight of active ingredient, even more preferably between 10 and 70% by weight.

The inventive active ingredients or compositions can be used as such or, depending on their particular physical and/or chemical properties, in the form of their formulations or the use forms prepared therefrom, such as aerosols, capsule suspensions, cold-fogging concentrates, warm-fogging concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment of seed, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, pastes, pesticide coated seed, suspension concentrates, suspoemulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble granules or tablets, water-soluble powders for the treatment of seed, wettable powders, natural and synthetic substances impregnated with active ingredient, and also microencapsulations in polymeric substances and in coating materials for seed, and also ULV cold-fogging and warm-fogging formulations.

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, emulsifier, dispersant, and/or binder or fixative, wetting agent, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, dyes and pigments, antifoams, preservatives, secondary thickeners, adhesives, giberellins and also further processing auxiliaries.

The inventive compositions include not only formulations which are already ready for use and can be applied with a suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water prior to use.

The inventive active ingredients may be present as such or in their (commercial) formulations and in the use forms prepared from these formulations as a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.

The inventive treatment of the plants and plant parts with the active ingredients or compositions is effected directly or by action on their surroundings, habitat or storage space by the customary treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, watering (drenching), drip irrigating and, in the case of propagation material, especially in the case of seeds, also by dry seed treatment, wet seed treatment, slurry seed treatment, incrustation, coating with one or more coats, etc. It is also possible to deploy the active ingredients by the ultra-low volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.

The invention further comprises a method for treating seed.

The invention further relates to seed which has been treated by one of the methods described in the previous paragraph. The inventive seeds are employed in methods for the protection of seed from unwanted microorganisms. In these methods, seed treated with at least one inventive active ingredient is used.

The inventive active ingredients or compositions are also suitable for treating seed. A large part of the damage to crop plants caused by harmful organisms is triggered by the infection of the seed during storage or after sowing, and also during and after germination of the plant. This phase is particularly critical since the roots and shoots of the growing plant are particularly sensitive, and even minor damage may result in the death of the plant. There is therefore a great interest in protecting the seed and the germinating plant by using appropriate compositions.

The control of phytopathogenic fungi by treating the seed of plants has been known for a long time and is the subject of constant improvements. However, the treatment of seed entails a series of problems which cannot always be solved in a satisfactory manner. For instance, it is desirable to develop methods for protecting the seed and the germinating plant, which dispense with, or at least significantly reduce, the additional deployment of crop protection compositions after planting or after emergence of the plants. It is also desirable to optimize the amount of the active ingredient used so as to provide the best possible protection for the seed and the germinating plant from attack by phytopathogenic fungi, but without damaging the plant itself by the active ingredient employed. In particular, methods for the treatment of seed should also take account of the intrinsic fungicidal properties of transgenic plants in order to achieve optimal protection of the seed and the germinating plant with a minimum expenditure of crop protection compositions.

The present invention therefore also relates to a method for protection of seed and germinating plants from attack by phytopathogenic fungi, by treating the seed with an inventive composition. The invention likewise relates to the use of the inventive compositions for treatment of seed to protect the seed and the germinating plant from phytopathogenic fungi. The invention further relates to seed which has been treated with an inventive composition for protection from phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergence is effected primarily by treating the soil and the above-ground parts of plants with crop protection compositions. Owing to the concerns regarding a possible influence of the crop protection compositions on the environment and the health of humans and animals, there are efforts to reduce the amount of active ingredients deployed.

One of the advantages of the present invention is that the particular systemic properties of the inventive active ingredients and compositions mean that treatment of the seed with these active ingredients and compositions not only protects the seed itself, but also the resulting plants after emergence, from phytopathogenic fungi. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter can be dispensed with.

It is likewise considered to be advantageous that the inventive active ingredients or compositions can especially also be used with transgenic seed, in which case the plant growing from this seed is capable of expressing a protein which acts against pests. By virtue of the treatment of such seed with the inventive active ingredients or compositions, merely the expression of the protein, for example an insecticidal protein, can control certain pests. Surprisingly, a further synergistic effect can be observed in this case, which additionally increases the effectiveness for protection against attack by pests.

The inventive compositions are suitable for protecting seed of any plant variety which is used in agriculture, in greenhouses, in forests or in horticulture and viticulture. In particular, this is the seed of cereals (such as wheat, barley, rye, triticale, sorghum/millet and oats), maize, cotton, soya beans, rice, potatoes, sunflower, bean, coffee, beet (for example sugar beet and fodder beet), peanut, oilseed rape, poppy, olive, coconut, cocoa, sugar cane, tobacco, vegetables (such as tomato, cucumbers, onions and lettuce), turf and ornamentals (see also below). The treatment of the seed of cereals (such as wheat, barley, rye, triticale and oats), maize and rice is of particular significance.

As also described below, the treatment of transgenic seed with the inventive active ingredients or compositions is of particular significance. This relates to the seed of plants containing at least one heterologous gene which enables the expression of a polypeptide or protein having insecticidal properties. The heterologous gene in transgenic seed can originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. This heterologous gene preferably originates from Bacillus sp., in which case the gene product is effective against the European corn borer and/or the Western corn rootworm. The heterologous gene more preferably originates from Bacillus thuringiensis.

In the context of the present invention, the inventive composition is applied to the seed alone or in a suitable formulation. Preferably, the seed is treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment. In general, the seed can be treated at any time between harvest and sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content of less than 15% by weight. Alternatively, it is also possible to use seed which, after drying, for example, has been treated with water and then dried again.

When treating the seed, care must generally be taken that the amount of the inventive composition applied to the seed and/or the amount of further additives is selected such that the germination of the seed is not impaired, or that the resulting plant is not damaged. This has to be borne in mind in particular in the case of active ingredients which can have phytotoxic effects at certain application rates.

The inventive compositions can be applied directly, i.e. without containing any other components and without having been diluted. In general, it is preferable to apply the compositions to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: U.S. Pat. No. 4,272,417, U.S. Pat. No. 4,245,432, U.S. Pat. No. 4,808,430, U.S. Pat. No. 5,876,739, US 2003/0176428 A1, WO 2002/080675, WO 2002/028186.

The active ingredients usable in accordance with the invention can be converted to the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seed, and also ULV formulations.

These formulations are prepared in a known manner, by mixing the active ingredients with customary additives, for example customary extenders and also solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, giberellins and also water.

Useful dyes which may be present in the seed dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.

Useful wetting agents which may be present in the seed dressing formulations usable in accordance with the invention are all substances which promote wetting and which are conventionally used for the formulation of active agrochemical ingredients. Preference is given to using alkyl naphthalenesulphonates, such as diisopropyl or diisobutyl naphthalenesulphonates.

Useful dispersants and/or emulsifiers which may be present in the seed dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agrochemical ingredients. Preference is given to using nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Suitable nonionic dispersants include especially ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ether, and the phosphated or sulphated derivatives thereof. Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehyde condensates.

Antifoams which may be present in the seed dressing formulations usable in accordance with the invention are all foam-inhibiting substances conventionally used for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.

Preservatives which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.

Secondary thickeners which may be present in the seed dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.

Adhesives which may be present in the seed dressing formulations usable in accordance with the invention are all customary binders usable in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.

The giberellins which may be present in the seed dressing formulations usable in accordance with the invention may preferably be giberellins A1, A3 (=gibberellic acid), A4 and A7; particular preference is given to using gibberellic acid. The giberellins are known (cf. R. Wegler “Chemie der Pflanzenschutz- and Schädlings-bekämpfungsmittel”, vol. 2, Springer Verlag, 1970, p. 401-412).

The seed dressing formulations usable in accordance with the invention can be used, either directly or after previously having been diluted with water, for the treatment of a wide range of different seed, including the seed of transgenic plants. In this case, additional synergistic effects may also occur in interaction with the substances formed by expression.

For treatment of seed with the seed dressing formulations usable in accordance with the invention, or the preparations prepared therefrom by adding water, all mixing units usable customarily for the seed dressing are useful. Specifically, the procedure in the seed dressing is to place the seed into a mixer, to add the particular desired amount of seed dressing formulations, either as such or after prior dilution with water, and to mix everything until the formulation is distributed homogeneously on the seed. If appropriate, this is followed by a drying operation.

The inventive active ingredients or compositions have potent microbicidal activity and can be used for control of unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

Fungicides can be used in crop protection for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection for control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

The inventive fungicidal compositions can be used for curative or protective control of phytopathogenic fungi. The invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.

The inventive compositions for controlling phytopathogenic fungi in crop protection comprise an effective but non-phytotoxic amount of the inventive active ingredients. An “effective but non-phytotoxic amount” means an amount of the inventive composition which is sufficient to control the fungal disease of the plant in a satisfactory manner or to eradicate the fungal disease completely, and which, at the same time, does not cause any significant symptoms of phytotoxicity. In general, this application rate may vary within a relatively wide range. It depends on several factors, for example on the fungus to be controlled, the plant, the climatic conditions and the ingredients of the inventive compositions.

The fact that the active ingredients are well tolerated by plants at the concentrations required for controlling plant diseases allows the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

All plants and plant parts can be treated in accordance with the invention. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which are protectable and non-protectable by plant breeders' rights. Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples of which include leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.

The inventive active ingredients, when they are well tolerated by plants, have favourable homeotherm toxicity and are well tolerated by the environment, are suitable for protecting plants and plant organs, for enhancing harvest yields, for improving the quality of the harvested material. They can preferably be used as crop protection compositions. They are active against normally sensitive and resistant species and against all or some stages of development.

Plants which can be treated in accordance with the invention include the following main crop plants: maize, soya bean, cotton, Brassica oil seeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassica carinata, rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet and sorghum, triticale, flax, grapes and various fruit and vegetables from various botanic taxa, for example Rosaceae sp. (for example pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds and peaches, and berry fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceae sp., Musaceae sp. (for example banana trees and plantations), Rubiaceae sp. (for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example lemons, oranges and grapefruit); Solanaceae sp. (for example tomatoes, potatoes, peppers, aubergines), Liliaceae sp., Compositae sp. (for example lettuce, artichokes and chicory—including root chicory, endive or common chicory), Umbelliferae sp. (for example carrots, parsley, celery and celeriac), Cucurbitaceae sp. (for example cucumbers—including gherkins, pumpkins, watermelons, calabashes and melons), Alliaceae sp. (for example leeks and onions), Cruciferae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, horseradish, cress and chinese cabbage), Leguminosae sp. (for example peanuts, peas, and beans—for example common beans and broad beans), Chenopodiaceae sp. (for example Swiss chard, fodder beet, spinach, beetroot), Malvaceae (for example okra), Asparagaceae (for example asparagus); useful plants and ornamental plants in the garden and woods; and in each case genetically modified types of these plants.

As already mentioned above, it is possible to treat all plants and their parts in accordance with the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above. More preferably, plants of the plant cultivars which are commercially available or are in use are treated in accordance with the invention. Plant cultivars are understood to mean plants which have new properties (“traits”) and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes.

The inventive treatment method can be used for the treatment of genetically modified organisms (GMOs), for example plants or seeds. Genetically modified plants (or transgenic plants) are plants in which a heterologous gene has been integrated stably into the genome. The expression “heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which is/are present in the plant (using for example antisense technology, cosuppression technology or RNAi technology [RNA interference]). A heterologous gene present in the genome is also called a transgene. A transgene that is defined by its specific presence in the plant genome is called a transformation or transgenic event.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. For example, the following effects exceeding the effects actually to be expected are possible: reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active ingredients and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf colour, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processibility of the harvested products.

At certain application rates, the inventive active ingredient combinations may also have a fortifying effect on plants. Accordingly, they are suitable for mobilizing the defence system of the plant against attack by unwanted phytopathogenic fungi and/or microorganisms and/or viruses. This may be one of the reasons for the enhanced activity of the inventive combinations, for example against fungi. Plant-fortifying (resistance-inducing) substances shall be understood to mean, in the present context, also those substances or combinations of substances which are capable of stimulating the defence system of plants in such a way that, when subsequently inoculated with unwanted phytopathogenic fungi, the plants treated display a substantial degree of resistance to these unwanted phytopathogenic fungi. The inventive substances can therefore be used for protection of plants from attack by the pathogens mentioned within a certain period of time after the treatment. The period within which protection is achieved generally extends for from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active ingredients.

Plants and plant varieties which are preferably treated according to the invention include all plants which have genetic material which imparts particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).

Plants and plant varieties which are also preferably treated in accordance with the invention are resistant to one or more biotic stress factors, i.e. said plants have a better defence against animal and microbial pests, such as to nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode-resistant plants are described, for example, in the following U.S. patent application Ser. Nos. 11/765,491, 11/765,494, 10/926,819, 10/782,020, 12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396 and 12/497,221.

Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stress factors. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, waterlogging, increased soil salinity, increased exposure to minerals, exposure to ozone, exposure to strong light, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients or shade avoidance.

Plants and plant cultivars which can likewise be treated in accordance with the invention are those plants which are characterized by enhanced yield characteristics. Enhanced yield in these plants may be the result of, for example, improved plant physiology, improved plant growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can also be affected by improved plant architecture (under stress and non-stress conditions), including early flowering, flowering control for hybrid seed production, seedling vigour, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processibility and better storage stability.

Plants that may be treated according to the invention are hybrid plants that already express the characteristics of heterosis, or hybrid effect, which results in generally higher yield, vigour, better health and resistance towards biotic and abiotic stress factors. Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male-fertile parent line (the male parent). The hybrid seed is typically harvested from the male-sterile plants and sold to growers. Male-sterile plants can sometimes (for example in corn) be produced by detasseling (i.e. mechanical removal of the male reproductive organs or male flowers); however, it is more typical for male sterility to be the result of genetic determinants in the plant genome. In that case, and especially when seed is the desired product to be harvested from the hybrid plants, it is typically beneficial to ensure that male fertility in hybrid plants, which contain the genetic determinants responsible for male sterility, is fully restored. This can be accomplished by ensuring that the male parents have appropriate fertility restorer genes which are capable of restoring the male fertility in hybrid plants that contain the genetic determinants responsible for male sterility. Genetic determinants for male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) were for instance described for Brassica species. However, genetic determinants for male sterility can also be located in the nuclear genome. Male-sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful means of obtaining male-sterile plants is described in WO 89/10396, in which, for example, a ribonuclease such as a bamase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.

Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, i.e. plants which have been made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate by various methods. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene which encodes the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science, 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genes encoding a petunia EPSPS (Shah et al., 1986, Science 233, 478-481), a tomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289) or an Eleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxidoreductase enzyme. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally occurring mutations of the abovementioned genes. Plants which express EPSPS genes which impart glyphosate tolerance have been described. Plants which express other genes which impart glyphosate tolerance, for example decarboxylase genes, have been described.

Other herbicide-resistant plants are, for example, plants that have been made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition. One such efficient detoxifying enzyme is, for example, an enzyme encoding a phosphinothricin acetyltransferase (for example the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinothricin acetyltransferase have been described.

Further herbicide-tolerant plants are also plants that have been made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyse the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to HPPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated or chimeric HPPD enzyme, as described in WO 96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387 or U.S. Pat. No. 6,768,044. Tolerance to HPPD inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native HPPD enzyme by the HPPD inhibitor. Such plants are described in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme prephenate dehydrogenase in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928. In addition, plants can be made more tolerant to HPPD inhibitors by inserting into the genome thereof a gene which encodes an enzyme which metabolizes or degrades HPPD inhibitors, for example CYP450 enzymes (see WO 2007/103567 and WO 2008/150473).

Further herbicide-resistant plants are plants that have been made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitors include, for example, sulphonylurea, imidazolinone, triazolopyrimidines, pyrimidinyl oxy(thio)benzoates, and/or sulphonylaminocarbonyltriazolinone herbicides. It is known that different mutations in the ALS enzyme (also known as acetohydroxy acid synthase, AHAS) confer tolerance to different herbicides and groups of herbicides, as described, for example, in Tranel and Wright (Weed Science 2002, 50, 700-712). The production of sulphonylurea-tolerant plants and imidazolinone-tolerant plants has been described. Further sulphonylurea- and imidazolinone-tolerant plants have also been described.

Further plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, by selection in cell cultures in the presence of the herbicide or by mutation breeding (cf., for example, for soya beans U.S. Pat. No. 5,084,082, for rice WO 97/41218, for sugar beet U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce U.S. Pat. No. 5,198,599 or for sunflower WO 01/065922).

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation which imparts such insect resistance.

In the present context, the term “insect-resistant transgenic plant” includes any plant containing at least one transgene comprising a coding sequence encoding:

1) an insecticidal crystal protein from Bacillus thuringiensis or an insecticidal portion thereof, such as the insecticidal crystal proteins compiled by Crickmore et al. (Microbiology and Molecular Biology Reviews 1998, 62, 807-813), updated by Crickmore et al. (2005) in the Bacillus thuringiensis toxin nomenclature, online at: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or insecticidal portions thereof, for example proteins of the Cry protein classes Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab, Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP-A 1999141 and WO 2007/107302), or those proteins encoded by synthetic genes as described in U.S. patent application Ser. No. 12/249,016; or 2) a crystal protein from Bacillus thuringiensis or a portion thereof which is insecticidal in the presence of a second crystal protein other than Bacillus thuringiensis or a portion thereof, such as the binary toxin made up of the Cy34 and Cy35 crystal proteins (Nat. Biotechnol. 2001, 19, 668-72; Applied Environm. Microbiol. 2006, 71, 1765-1774) or the binary toxin made up of the Cry1A or Cry1F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S. patent application Ser. No. 12/214,022 and EP08010791.5); or 3) a hybrid insecticidal protein comprising parts of two different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above, for example the Cry1A.105 protein produced by maize event MON98034 (WO 2007/027777); or 4) a protein of any one of points 1) to 3) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes induced in the encoding DNA during cloning or transformation, such as the Cry3Bb1 protein in maize events MON863 or MON88017, or the Cry3A protein in maize event MIR604; or 5) an insecticidal secreted protein from Bacillus thuringiensis or Bacillus cereus, or an insecticidal portion thereof, such as the vegetative insecticidal proteins (VIP) listed at: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html, for example proteins from the VIP3Aa protein class; or 6) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin made up of the VIP1A and VIP2A proteins (WO 94/21795); or 7) a hybrid insecticidal protein comprising parts from different secreted proteins from Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins in 1) above or a hybrid of the proteins in 2) above; or 8) a protein of any one of points 5) to 7) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes induced in the encoding DNA during cloning or transformation (while still encoding an insecticidal protein), such as the VIP3Aa protein in cotton event COT 102; or 9) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a crystal protein from Bacillus thuringiensis, such as the binary toxin made up of the proteins VIP3 and Cry1A or Cry1F (U.S. patent applications 61/126,083 and 61/195,019), or the binary toxin made up of the VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S. patent application Ser. No. 12/214,022 and EP 08010791.5); or 10) a protein according to point 9) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes induced in the encoding DNA during cloning or transformation (while still encoding an insecticidal protein).

Of course, insect-resistant transgenic plants, as used herein, also include any plant comprising a combination of genes encoding the proteins of any one of the abovementioned classes 1 to 10. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any one of the abovementioned classes 1 to 10, to expand the range of target insect species affected or to delay insect resistance development to the plants, by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect.

In the present context, an “insect-resistant transgenic plant” additionally includes any plant containing at least one transgene comprising a sequence for production of double-stranded RNA which, after consumption of food by an insect pest, prevents the growth of this pest.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stress factors. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress-tolerant plants include the following:

a. plants which contain a transgene capable of reducing the expression and/or the activity of the poly(ADP-ribose)polymerase (PARP) gene in the plant cells or plants;

b. plants which contain a stress tolerance-enhancing transgene capable of reducing the expression and/or the activity of the PARG-encoding genes of the plants or plant cells;

c. plants which contain a stress tolerance-enhancing transgene coding for a plant-functional enzyme of the nicotinamide adenine dinucleotide salvage biosynthesis pathway, including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyltransferase, nicotinamide adenine dinucleotide synthetase or nicotinamide phosphoribosyltransferase.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as:

1) Transgenic plants which synthesize a modified starch which is altered with respect to its chemophysical traits, in particular the amylose content or the amylose/amylopectin ratio, the degree of branching, the average chain length, the distribution of the side chains, the viscosity behaviour, the gel resistance, the grain size and/or grain morphology of the starch in comparison to the synthesized starch in wild-type plant cells or plants, such that this modified starch is better suited for certain applications. 2) Transgenic plants which synthesize non-starch carbohydrate polymers or which synthesize non-starch carbohydrate polymers with altered properties in comparison to wild-type plants without genetic modification. Examples are plants which produce polyfructose, especially of the inulin and levan type, plants which produce alpha-1,4-glucans, plants which produce alpha-1,6-branched alpha-1,4-glucans, and plants producing alternan. 3) Transgenic plants which produce hyaluronan. 4) Transgenic plants or hybrid plants such as onions with particular properties, such as “high soluble solids content”, “low pungency” (LP) and/or “long storage” (LS).

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fibre characteristics. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such altered fibre characteristics, and include:

a) plants, such as cotton plants, which contain an altered form of cellulose synthase genes;

b) plants, such as cotton plants, which contain an altered form of rsw2 or rsw3 homologous nucleic acids, such as cotton plants with an increased expression of sucrose phosphate synthase;

c) plants, such as cotton plants, with an increased expression of sucrose synthase;

d) plants, such as cotton plants, wherein the timing of the plasmodesmatal gating at the basis of the fibre cell is altered, for example through downregulation of fibre-selective β-1,3-glucanase;

e) plants, such as cotton plants, which have fibres with altered reactivity, for example through expression of the N-acetylglucosaminetransferase gene, including nodC, and chitin synthase genes.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such altered oil characteristics, and include:

a) plants, such as oilseed rape plants, which produce oil having a high oleic acid content;

b) plants, such as oilseed rape plants, which produce oil having a low linolenic acid content;

c) plants, such as oilseed rape plants, which produce oil having a low level of saturated fatty acids.

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants such as potatoes which are virus-resistant, for example to the potato virus Y (SY230 and SY233 events from Tecnoplant, Argentina), or which are resistant to diseases such as potato late blight (e.g. RB gene), or which exhibit reduced cold-induced sweetness (which bear the genes Nt-Inh, II-INV) or which exhibit the dwarf phenotype (A-20 oxidase gene).

Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such altered characteristics, and include plants such as oilseed rape with retarded or reduced seed shattering.

Particularly useful transgenic plants which can be treated according to the invention are plants with transformation events or combinations of transformation events which are the subject of granted or pending petitions for nonregulated status in the USA at the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA). Information relating to this is available at any time from APHIS (4700 River Road Riverdale, Md. 20737, USA), for example via the website http://www.aphis.usda.gov/brs/not_reg.html. At the filing date of this application, the petitions with the following information were either granted or pending at the APHIS:

-   -   Petition: Identification number of the petition. The technical         description of the transformation event can be found in the         specific petition document available from APHIS on the website         via the petition number. These descriptions are hereby disclosed         by reference.     -   Extension of a petition: Reference to an earlier petition for         which an extension of scope or term is being requested.     -   Institution: Name of the person submitting the petition.     -   Regulated article: The plant species in question.     -   Transgenic phenotype: The trait imparted to the plant by the         transformation event.     -   Transformation event or line: The name of the event(s)         (sometimes also referred to as line(s)) for which nonregulated         status is being requested.     -   APHIS documents: Various documents which have been published by         APHIS with regard to the petition or can be obtained from APHIS         on request.

Particularly useful transgenic plants which may be treated according to the invention are plants which comprise one or more genes which encode one or more toxins, and are the transgenic plants which are sold under the following trade names: YIELD GARD® (for example corn, cotton, soybeans), KnockOut® (for example corn), BiteGard® (for example corn), BT-Xtra® (for example corn), StarLink® (for example corn), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example corn), Protecta® and NewLeaf® (potato). Examples of herbicide-tolerant plants which should be mentioned are corn varieties, cotton varieties and soybean varieties which are available under the following trade names: Roundup Ready® (tolerance to glyphosate, for example corn, cotton, soybeans), Liberty Link® (tolerance to phosphinothricin, for example oilseed rape), IMI® (tolerance to imidazolinone) and SCS® (tolerance to sulphonylurea, for example corn). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which should be mentioned include the varieties sold under the Clearfield® name (for example corn).

Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or a combination of transformation events, and that are listed for example in the databases for various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://ceragmc.org/index.php?evidcode=&hstIDXCode=&gType=&AbbrCode=&atCode=&stCode=&coIDCode=&action=gm_crop_database&modeSubmit).

The inventive active ingredients or compositions can also be used in the protection of materials, for protection of industrial materials against attack and destruction by unwanted microorganisms, for example fungi and insects.

In addition, the inventive compounds can be used as antifouling compositions, alone or in combinations with other active ingredients.

Industrial materials in the present context are understood to mean inanimate materials which have been prepared for use in industry. For example, industrial materials which are to be protected by inventive active ingredients from microbial alteration or destruction may be adhesives, sizes, paper, wallpaper and cardboard, textiles, carpets, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with or destroyed by microorganisms. The range of materials to be protected also includes parts of production plants and buildings, for example cooling water circuits, cooling and heating systems, and ventilation and air conditioning systems, which may be impaired by the proliferation of microorganisms. Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and cardboard, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood. The inventive active ingredients or compositions may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould. In addition, the inventive compounds can be used to protect objects which come into contact with saltwater or brackish water, especially hulls, screens, nets, buildings, moorings and signalling systems, from fouling.

The inventive method for controlling unwanted fungi can also be employed for protecting storage goods. Storage goods are understood to mean natural substances of vegetable or animal origin or processed products thereof which are of natural origin, and for which long-term protection is desired. Storage goods of vegetable origin, for example plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, can be protected freshly harvested or after processing by (pre)drying, moistening, comminuting, grinding, pressing or roasting. Storage goods also include timber, both unprocessed, such as construction timber, electricity poles and barriers, or in the form of finished products, such as furniture. Storage goods of animal origin are, for example, hides, leather, furs and hairs. The inventive active ingredients may prevent adverse effects, such as rotting, decay, discoloration, decoloration or formation of mould.

Non-limiting examples of pathogens of fungal diseases which can be treated in accordance with the invention include:

diseases caused by powdery mildew pathogens, for example Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator; diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, for example Puccinia recondita or Puccinia triticina; Uromyces species, for example Uromyces appendiculatus; diseases caused by pathogens from the group of the Oomycetes, for example Bremia species, for example Bremia lactucae; Peronospora species, for example Peronospora pisi or P. brassicae; Phytophthora species, for example Phytophthora infestans; Plasmopara species, for example Plasmopara viticola; Pseudoperonospora species, for example Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, for example Pythium ultimum; leaf blotch diseases and leaf wilt diseases caused, for example, by Alternaria species, for example Alternaria solani; Cercospora species, for example Cercospora beticola; Cladiosporium species, for example Cladiosporium cucumerinum; Cochliobolus species, for example Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium); Colletotrichum species, for example Colletotrichum lindemuthanium; cycloconium species, for example cycloconium oleaginum; Diaporthe species, for example Diaporthe citri; Elsinoe species, for example Elsinoe fawcettii; Gloeosporium species, for example Gloeosporium laeticolor; Glomerella species, for example Glomerella cingulata; Guignardia species, for example Guignardia bidwelli; Leptosphaeria species, for example Leptosphaeria maculans; Magnaporthe species, for example Magnaporthe grisea; Microdochium species, for example Microdochium nivale; Mycosphaerella species, for example Mycosphaerella graminicola and M. fijiensis; Phaeosphaeria species, for example Phaeosphaeria nodorum; Pyrenophora species, for example Pyrenophora teres; Ramularia species, for example Ramularia collo-cygni; Rhynchosporium species, for example Rhynchosporium secalis; Septoria species, for example Septoria apii; Typhula species, for example Typhula incarnate; Venturia species, for example Venturia inaequalis; root and stem diseases caused, for example, by Corticium species, for example Corticium graminearum; Fusarium species, for example Fusarium oxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis; Rhizoctonia species, such as, for example Rhizoctonia solani; Tapesia species, for example Tapesia acuformis; Thielaviopsis species, for example Thielaviopsis basicola; ear and panicle diseases (including corn cobs) caused, for example, by Alternaria species, for example Alternaria spp.; Aspergillus species, for example Aspergillus flavus; Cladosporium species, for example Cladosporium cladosporioides; Claviceps species, for example Claviceps purpurea; Fusarium species, for example Fusarium culmorum; Gibberella species, for example Gibberella zeae; Monographella species, for example Monographella nivalis; Septoria species, for example Septoria nodorum; diseases caused by smut fungi, for example Sphacelotheca species, for example Sphacelotheca reiliana; Tilletia species, for example Tilletia caries, T. controversa; Urocystis species, for example Urocystis occulta; Ustilago species, for example Ustilago nuda, U. nuda tritici; fruit rot caused, for example, by Aspergillus species, for example Aspergillus flavus; Botrytis species, for example Botrytis cinerea; Penicillium species, for example Penicillium expansum and P. purpurogenum; Sclerotinia species, for example Sclerotinia sclerotiorum; Verticilium species, for example Verticilium alboatram; seed- and soil-borne rot and wilt diseases, and also diseases of seedlings, caused, for example, by Fusarium species, for example Fusarium culmorum; Phytophthora species, for example Phytophthora cactorum; Pythium species, for example Pythium ultimum; Rhizoctonia species, for example Rhizoctonia solani; Sclerotium species, for example Sclerotium rolfsii; cancers, galls and witches' broom caused, for example, by Nectria species, for example Nectria galligena; wilt diseases caused, for example, by Monilinia species, for example Monilinia laxa; deformations of leaves, flowers and fruits caused, for example, by Taphrina species, for example Taphrina deformans; degenerative diseases of woody plants caused, for example, by Esca species, for example Phaeomoniella chlamydospora and Phaeoacremonium aleophilum and Fomitiporia mediterranea; diseases of flowers and seeds caused, for example, by Botrytis species, for example Botrytis cinerea; diseases of plant tubers caused, for example, by Rhizoctonia species, for example Rhizoctonia solani; Helminthosporium species, for example Helminthosporium solani; diseases caused by bacterial pathogens, for example Xanthomonas species, for example Xanthomonas campestris pv. oryzae; Pseudomonas species, for example Pseudomonas syringae pv. lachrymans; Erwinia species, for example Erwinia amylovora.

The following diseases of soya beans can be controlled with preference:

Fungal diseases on leaves, stems, pods and seeds caused, for example, by Alternaria leaf spot (Alternaria spec. atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), Choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), pod and stem blight (Phomopsis sojae), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), target spot (Corynespora cassiicola).

Fungal diseases on roots and the stem base caused, for example, by black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

Microorganisms capable of degrading or altering the industrial materials include, for example, bacteria, fungi, yeasts, algae and slime organisms. The inventive active ingredients preferably act against fungi, especially moulds, wood-discoloring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae. Examples include microorganisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, such as Trichoderma virile; Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus, such as Staphylococcus aureus.

In addition, the inventive active ingredients also have very good antimycotic activity. They have a very broad antimycotic activity spectrum, especially against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as Candida albicans, Candida glabrata), and Epidermophyton floceosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi by no means constitutes a restriction of the mycotic spectrum covered, and is merely of illustrative character.

The inventive active ingredients can therefore be used both in medical and in non-medical applications.

When using the inventive active ingredients as fungicides, the application rates can be varied within a relatively wide range, depending on the kind of application. The application rate of the inventive active ingredients is

-   -   in the case of treatment of plant parts, for example leaves:         from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more         preferably from 50 to 300 g/ha (in the case of application by         watering or dripping, it is even possible to reduce the         application rate, especially when inert substrates such as         rockwool or perlite are used);     -   in the case of seed treatment: from 2 to 200 g per 100 kg of         seed, preferably from 3 to 150 g per 100 kg of seed, more         preferably from 2.5 to 25 g per 100 kg of seed, even more         preferably from 2.5 to 12.5 g per 100 kg of seed;     -   in the case of soil treatment: from 0.1 to 10 000 g/ha,         preferably from 1 to 5000 g/ha.

These application rates are merely by way of example and are not limiting for the purposes of the invention.

The inventive active ingredients or compositions can thus be used to protect plants from attack by the pathogens mentioned for a certain period of time after treatment. The period for which protection is provided extends generally for 1 to 28 days, preferably for 1 to 14 days, more preferably for 1 to 10 days, even more preferably for 1 to 7 days, after the treatment of the plants with the active ingredients, or for up to 200 days after a seed treatment.

In addition, the inventive treatment can reduce the mycotoxin content in the harvested material and the foods and feeds prepared therefrom. Mycotoxins include particularly, but not exclusively, the following: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin, fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins which can be produced, for example, by the following fungi: Fusarium spec., such as Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F. garaminearum (Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudograndnearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides, inter alia, and also by Aspergillus spec., Penicillium spec. Claviceps purpurea, Stachybotrys spec., inter alia.

In some cases, the inventive compounds can, at particular concentrations or application rates, also be used as herbicides, safeners, growth regulators or compositions to improve plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including compositions against viroids) or as compositions against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). If appropriate, they can also be used as intermediates or precursors for the synthesis of other active ingredients.

The inventive active ingredients intervene in the metabolism of the plants and can therefore also be used as growth regulators.

Plant growth regulators may exert various effects on plants. The effects of the substances depend essentially on the time of application relative to the development stage of the plant and on the amounts of active ingredient applied to the plants or their environment and on the type of application. In each case, growth regulators should have a particular desired effect on the crop plants.

Plant growth-regulating compounds can be used, for example, to inhibit the vegetative growth of the plants. Such inhibition of growth is of economic interest, for example, in the case of grasses, since it is thus possible to reduce the frequency of grass cutting in ornamental gardens, parks and sport facilities, on roadsides, at airports or in fruit crops. Also of significance is the inhibition of the growth of herbaceous and woody plants on roadsides and in the vicinity of pipelines or overhead cables, or quite generally in areas where vigorous plant growth is unwanted.

Also important is the use of growth regulators for inhibition of the longitudinal growth of cereal. This reduces or completely eliminates the risk of lodging of the plants prior to harvest. In addition, growth regulators in the case of cereals can strengthen the culm, which also counteracts lodging. The employment of growth regulators for shortening and strengthening culms allows the deployment of higher fertilizer volumes to increase the yield, without any risk of lodging of the cereal crop.

In many crop plants, inhibition of vegetative growth allows denser planting, and it is thus possible to achieve higher yields based on the soil surface. Another advantage of the smaller plants obtained in this way is that the crop is easier to cultivate and harvest.

Inhibition of the vegetative plant growth may also lead to enhanced yields because the nutrients and assimilates are of more benefit to flower and fruit formation than to the vegetative parts of the plants.

Frequently, growth regulators can also be used to promote vegetative growth. This is of great benefit when harvesting the vegetative plant parts. However, promoting vegetative growth may also promote generative growth in that more assimilates are formed, resulting in more or larger fruits.

In some cases, yield increases may be achieved by manipulating the metabolism of the plant, without any detectable changes in vegetative growth. In addition, growth regulators can be used to alter the composition of the plants, which in turn may result in an improvement in quality of the harvested products. For example, it is possible to increase the sugar content in sugar beet, sugar cane, pineapples and in citrus fruit, or to increase the protein content in soya or cereals. It is also possible, for example, to use growth regulators to inhibit the degradation of desirable ingredients, for example sugar in sugar beet or sugar cane, before or after harvest. It is also possible to positively influence the production or the elimination of secondary plant ingredients. One example is the stimulation of the flow of latex in rubber trees.

Under the influence of growth regulators, parthenocarpic fruits may be formed. In addition, it is possible to influence the sex of the flowers. It is also possible to produce sterile pollen, which is of great importance in the breeding and production of hybrid seed.

Use of growth regulators can control the branching of the plants. On the one hand, by breaking apical dominance, it is possible to promote the development of side shoots, which may be highly desirable particularly in the cultivation of ornamental plants, also in combination with an inhibition of growth. On the other hand, however, it is also possible to inhibit the growth of the side shoots. This effect is of particular interest, for example, in the cultivation of tobacco or in the cultivation of tomatoes.

Under the influence of growth regulators, the amount of leaves on the plants can be controlled such that defoliation of the plants is achieved at a desired time. Such defoliation plays a major role in the mechanical harvesting of cotton, but is also of interest for facilitating harvesting in other crops, for example in viticulture. Defoliation of the plants can also be undertaken to lower the transpiration of the plants before they are transplanted.

Growth regulators can likewise be used to regulate fruit dehiscence. On the one hand, it is possible to prevent premature fruit dehiscence. On the other hand, it is also possible to promote fruit dehiscence or even flower abortion to achieve a desired mass (“thinning”), in order to eliminate alternation. Alternation is understood to mean the characteristic of some fruit species, for endogenous reasons, to deliver very different yields from year to year. Finally, it is possible to use growth regulators at the time of harvest to reduce the forces required to detach the fruits, in order to allow mechanical harvesting or to facilitate manual harvesting.

Growth regulators can also be used to achieve faster or else delayed ripening of the harvested material before or after harvest. This is particularly advantageous as it allows optimal adjustment to the requirements of the market. Moreover, growth regulators in some cases can improve the fruit colour. In addition, growth regulators can also be used to concentrate maturation within a certain period of time. This establishes the prerequisites for complete mechanical or manual harvesting in a single operation, for example in the case of tobacco, tomatoes or coffee.

By using growth regulators, it is additionally possible to influence the resting of seed or buds of the plants, such that plants such as pineapple or ornamental plants in nurseries, for example, germinate, sprout or flower at a time when they are normally not inclined to do so. In areas where there is a risk of frost, it may be desirable to delay budding or germination of seeds with the aid of growth regulators, in order to avoid damage resulting from late frosts.

Finally, growth regulators can induce resistance of the plants to frost, drought or high salinity of the soil. This allows the cultivation of plants in regions which are normally unsuitable for this purpose.

The plants listed can be treated in accordance with the invention in a particularly advantageous manner with the compounds of the general formula (I) and/or the inventive compositions. The preferred ranges stated above for the active ingredients or compositions also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or compositions specifically mentioned in the present text.

The invention is illustrated by the examples below. However, the invention is not limited to the examples.

PREPARATION EXAMPLES Example 1

26.23 g [200 mmol] of N-methylsuccinamide are initially charged, 119 g [1000 mmol] of thionyl chloride are added dropwise at 5° C. and the mixture is stirred until a solution has formed. Then this solution is added dropwise to 119 g [1000 mmol] of thionyl chloride heated to 60° C. The mixture is then heated to 80° C. and stirred at this temperature for 1 hour. The reaction mixture is concentrated on a rotary evaporator. The residue (thick dark brown oil) is admixed with 150 ml of isobutanol and 50 ml of water and heated to 70° C. for 6 hours. The mixture is then allowed to cool to room temperature, and the precipitated solid is filtered off and washed with water and methanol. Drying results in 22.9 g of dark green solid which, according to HPLC analysis, contains 1.1% of the title compound.

Example 2

26.23 g [200 mmol] of N-methylsuccinamide are initially charged, 119 g [1000 mmol] of thionyl chloride are added dropwise at 5° C. and the mixture is stirred until a solution has formed. Then this solution is added dropwise to 119 g [1000 mmol] of thionyl chloride heated to 60° C. The mixture is then heated to 80° C. and stirred at this temperature for 1 hour. The reaction mixture is concentrated on a rotary evaporator. The residue (thick dark brown oil) is dissolved in 150 ml of toluene. 1 g of methyltrioctylammonium chloride (Aliquat 336) is added, the mixture is heated to approx. 70° C. and then 50 ml of water are added gradually. The mixture is stirred under reflux for 4 hours and cooled to room temperature, and the solid is filtered off with suction and washed with 50 ml of water and twice with 50 ml each time of ethanol. Drying results in 19.43 g of almost black solid which, according to HPLC analysis, contains 0.56% of the title compound.

Example 3 Step A

100 g of N-methylmaleimide (0.9 mol) and 218 g of Lawesson's reagent (0.54 mol) are heated to boiling in 1000 ml of absolute toluene for 30 min. A red suspension is obtained. The suspension is filtered with suction through silica gel and the mother liquor is cautiously concentrated. The product goes into the receiver as an azeotrope and turns the colour purple. The purple solution is concentrated gradually at 210 mbar to obtain, according to thin layer chromatography, 1 g (0.77%) of clean N-methyl-2-thio-5-oxopyffolidine product.

Step B

2.7 g of N-methyl-2-thio-5-oxopyrrolidine (21 mmol) and 3.8 g of pyridine (48 mmol) are initially charged in 100 ml of absolute methylene chloride. At room temperature, 12.6 g of thionyl chloride (106 mmol) are added and the mixture is heated to boiling for 12 h. After cooling, the greenish-brown solution is poured onto ice-water and extracted with methylene chloride, the organic phase is dried and concentrated, and the resulting greenish oil is purified by column chromatography. This gives 3.0 g (72%) of a mixture of 75% N-methyl-2-thio-3,4-dichloro-5-oxopyffolidine and 25% N-methyl-3,4-dichloromaleimide.

Step C

0.91 g (4.6 mmol) of the mixture of 75% N-methyl-2-thio-3,4-dichloro-5-oxopyrrolidine and 25% N-methyl-3,4-dichloromaleimide are initially charged in 10 ml of ethanol. At 70° C., a yellowish solution forms. 1.03 g (6.5 mmol) of sodium thiosulphate (dissolved in 10 ml water) are added dropwise at 70° C. and the mixture is stirred at this temperature for a further 1 h and then filtered with suction at room temperature. The dark brown residue is washed with 10 ml of water; yellow crystals precipitate out in the mother liquor. This gives 0.56 g (16%) of a mixture of various products, in which the monothio product is present to an extent of about 40% and the dithio products together to an extent of about 5% (1:1 mixture).

Chromatographic Isolation and Structures Elucidation

Analytical HPLC conditions Column: Zorbax Eclipse Plus C18 1.8μm 50 × 4.6 mm (L × ID) Column temperature: 55° C. Eluent A: 0.1% H₃PO₄ Eluent B: acetonitrile Gradient: 0′ % B = 10, 0.4′ % B = 10, 5.1′ % B = 95, 6.2′ % B = 95 Flow rate: 2.75 ml/min Injection volume: 1.7 μl Sample solution: 0.1% in acetonitrile Detection: UV absorption at 210 nm Preparative HPLC conditions Column: Kromasil 100 C18 16 μm 250 × 40 mm (L × ID) Column temperature: room temperature Eluent A: 0.5% HCOOH Eluent B: acetonitrile Gradient : 0′ % B = 45, 10′ % B = 45, 30′ % B = 90, 30.1′ % B = 100, 35′ % B = 100 Flow rate: 100 ml/min Injection volume: 4 ml Sample solution: 500 mg in 1,4-dioxane Detection: UV absorption at 210 nm Fraction Workup

The isolated fraction is diluted 1+2 with water and sucked through a Strata X33 Polymeric Sorbent 60 mg solid phase extraction cartridge within 45 min. The cartridge is dried with argon for 1 h and eluted with 1 ml of deutero-THF.

Spectroscopic Data

¹³C NMR (600 MHz, d8-THF): δ=24.2 (C-17), 27.5 (C-14), 127.5 (C-12), 130.3 (C-8), 132.4 (C-2), 135.8 (C-6), 165.2 (C-9+C-11), 167.0 (C-5), 194.0 (C-3) ppm.

¹³C NMR (600 MHz, d8-THF): δ=27.6 (C-14+C-17), 128.2 (C-2+C-12), 135.0 (C-6+C-8), 167.2 (C-5+C-9), 194.2 (C-3+C-11) ppm.

¹³C NMR (600 MHz, d8-THF): S=27.6 (C-32+C-35), 126.3 (C-20+C-26), 136.5 (C-24+C-30), 167.2 (C-23+C-29), 194.4 (C-21+C-27) ppm.

USE EXAMPLES Example A Phytophthora Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is mixed with the specified amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the active ingredient formulation at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabin at about 20° C. and 100% relative air humidity. Evaluation follows 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed. In this test, the following inventive compounds show, at an active ingredient concentration of 250 ppm, an efficacy of 70% or more:

TABLE A Phytophthora test (tomato)/protective Application Efficacy Active ingredient rate (ppm) (%)

250 72

Example B Plasmopara Test (Grapevine)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is mixed with the specified amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the active ingredient formulation at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in an incubation cabin at approx. 20° C. and 100% relative air humidity for 1 day. Subsequently, the plants are placed in a greenhouse at approx. 21° C. and approx. 90% air humidity for 4 days. The plants are then moistened and placed in an incubation cabin for 1 day. Evaluation follows 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed. In this test, the following inventive compounds show, at an active ingredient concentration of 250 ppm, an efficacy of 70% or more:

TABLE B Plasmopara test (grapevine)/protective Application Efficacy Active ingredient rate (ppm) (%)

250 83

Example C Venturia Test (Apple)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

-   -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is mixed with the specified amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the active ingredient formulation at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen Venturia inaequalis and then remain in an incubation cabin at approx. 20° C. and 100% relative air humidity for 1 day. The plants are then placed in a greenhouse at about 21° C. and a relative air humidity of approx. 90%. Evaluation follows 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed. In this test, the following inventive compounds show, at an active ingredient concentration of 250 ppm, an efficacy of 70% or more:

TABLE C Venturia test (apple)/protective Application Efficacy Active ingredient rate (ppm) (%)

250 99

250 71

Example D Alternaria Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate active ingredient formulation, 1 part by weight of active ingredient is mixed with the specified amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the active ingredient formulation at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants are then placed in an incubation cabin at approx. 20° C. and 100% relative air humidity. Evaluation follows 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed. In this test, the following inventive compounds show, at an active ingredient concentration of 250 ppm, an efficacy of 70% or more:

TABLE D Alternaria test (tomato)/protective Application Efficacy Active ingredient rate (ppm) (%)

250 95

250 76 

The invention claimed is:
 1. A compound of formula (I)

in which X¹ is O or S, X² is O or S, X³ is O or S, R¹ and R² are the same or different and are each hydrogen, C₁-C₈-alkyl which is optionally substituted with one or more halogen, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one ore more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, or are aryl or aryl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, COR⁴, or sulphonylamino, R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, R⁴ is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy, and salts thereof.
 2. The compound of claim 1, in which R¹ and R² are the same or different and are each hydrogen, C₁-C₆-alkyl which is optionally substituted with one or more fluorine, chlorine, bromine, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more chlorine, methyl, or trifluoromethyl, or are phenyl or phenyl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more fluorine, chlorine, bromine, methyl, trifluoromethyl, COR⁴, or sulphonylamino, R³ is hydrogen, methyl, ethyl, methylcarbonyl, ethylcarbonyl, or phenyl which is optionally substituted with one or more fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, or trifluoromethyl, R⁴ is hydroxyl, methyl, ethyl, methoxy or ethoxy.
 3. The compound of claim 1, in which R¹ and R² are each methyl.
 4. A compound of formula (I-a)

in which R¹ and R² are the same or different and are each hydrogen, C₁-C₈-alkyl which is optionally substituted with one or more halogen, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, or are aryl or aryl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, COR⁴, or sulphonylamino, R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, R⁴ is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy, and salts thereof.
 5. A compound of formula (I-b)

in which R¹ and R² are the same or different and are each hydrogen, C₁-C₈alkyl which is optionally substituted with one or more halogen, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, or are aryl or aryl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, COR⁴, or sulphonylamino, R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, R⁴ is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy, and salts thereof.
 6. A compound of formula (I-c)

in which R¹ and R² are the same or different and are each hydrogen, C₁-C₈-alkyl which is optionally substituted with one or more halogen, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, or are aryl or aryl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, COR⁴, or sulphonylamino, R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, R⁴ is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy, and salts thereof.
 7. A method for controlling phytopathogenic harmful fungi, comprising applying a compound of claim 1, 4, 5, or 6 to the phytopathogenic harmful fungi, their habitat, or combinations thereof.
 8. A composition for controlling phytopathogenic harmful fungi, comprising the compound of claim 1, 4, 5, or 6 and an extender, a surfactant, and combinations thereof.
 9. A process for producing a composition of claim 1, 4, 5, or 6, comprising mixing a compound of claim 1 with an extender, a surfactant, or combinations thereof.
 10. A process for preparing a compound of claim 1, 4, 5, or 6 comprising A) (1) reacting a succinic monoamide of formula (VI)

in which R is hydrogen, C₁-C₈-alkyl which is optionally substituted with one or more halogen, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, or aryl or aryl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, COR⁴, or sulphonylamino, with an excess of thionyl chloride, optionally in the presence of a diluent, (2) removing excess thionyl chloride to form a product mixture, (3) adding an organic solvent, water, and optionally a phase transfer catalyst to the product mixture, and (4) isolating a compound of claim 1 by a chromatography process, or B) reacting a dichloromaleimide of formula (VII)

in which R² is hydrogen, C₁-C₈-alkyl which is optionally substituted with one or more halogen, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, or aryl or aryl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, COR⁴, or sulphonylamino, and X³ is O or S, with a dichloromaleimide of formula (VIII)

in which R¹ is hydrogen, C₁-C₈-alkyl which is optionally substituted with one or more halogen, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl, or aryl or aryl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, COR⁴, or sulphonylamino, X¹ is O or S, and X² is O or S, and an inorganic thiosulphate in a solvent or solvent mixture.
 11. The compound of claim 4, 5, or 6, in which R¹ and R² are the same or different and are each hydrogen, C₁-C₆-alkyl which is optionally substituted with one or more fluorine, chlorine, bromine, OR³, or COR⁴, C₃-C₇-cycloalkyl which is optionally substituted with one or more chlorine, methyl, or trifluoromethyl, or are phenyl or phenyl-(C₁-C₄-alkyl) which in each case is optionally substituted with one or more fluorine, chlorine, bromine, methyl, trifluoromethyl, COR⁴, or sulphonylamino, R³ is hydrogen, methyl, ethyl, methylcarbonyl, ethylcarbonyl, or phenyl which is optionally substituted with one or more fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, or trifluoromethyl, R⁴ is hydroxyl, methyl, ethyl, methoxy or ethoxy.
 12. The compound of claim 4, 5, or 6 in which R¹ and R² are each methyl. 